N-Monosubstituted indoanilines

ABSTRACT

New dyestuffs are described for keratinic fibers which produce particularly luminous shades without the need for an oxidizing agent. These dyestuffs have the formula: ##STR1## or a tautomeric form thereof wherein each of R 1  and R 4 , which may be identical or different, represents a member selected from hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, acylamino and ureido; 
     each of R 2  and R 3 , which may be identical or different, represents a member selected from hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, amino, N-alkylamino, N-(hydroxyalkyl)-amino, N-(carbamyl-alkyl)-amino, acylamino and ureido, each of said alkyls containing 1 to 6 carbon atoms; 
     each of R 5  and R 6 , which may be identical or different, represents a member selected from hydrogen, halogen, alkyl containing 1 to 6 carbon atoms and alkoxy containing 1 to 6 carbon atoms, with the proviso that when R 5  and R 6  are both other than hydrogen at least one is in a meta-position relative to the NHR 7  group; and R 7  represents a member selected from alkyl, hydroxyalkyl, acylaminoalkyl, mesylaminoalkyl, carbamylalkyl, aminoalkyl, piperidinoalkyl and morpholinoalkyl, each of said alkyls containing 1 to 6 carbon atoms.

This is a division, of application Ser. No. 530,975 filed Dec. 9, 1974, U.S. Pat. No. 4,007,747.

The present invention relates to indoanilines in which the amino group in the 4'-position is monosubstituted.

It is known to dye keratin fibers, more particularly living human hair, by applying to the hair, in the presence of an oxidizing agent such as hydrogen peroxide, added at the time of use, a dyeing composition comprising a mixture, in a suitable cosmetic carrier, of compounds belonging to each of two categories. The first category of compounds, generally called "oxidation bases", comprises mainly para-phenylene-diamines or para-amino-phenols which lead, on oxidation, to para-benzoquinonediimines or to para-benzoquinone-monoimines. The second category of compounds, generally called "coupling agents", comprises meta-amino-phenols, meta-acetylamino-phenols, meta-diamines and meta-diphenols. They are compounds with which the benzoquinonemono or di-imines will react to give rise to dyestuffs called, depending on their structure, indophenols, indoanilines or indamines.

These dyestuffs, from which a range of exceptionally rich shades can be obtained, are primarily noted for the luminous nature and for the rich sheen attainable therewith. However, when a complex dyeing composition is used, that is to say a composition which comprises several bases and several coupling agents, it is often very difficult to predict the contribution which each possible combination of oxidation base and coupling agent will make to the final shade. In other words, firstly, it is very difficult at the start to make an exact prediction as to the final shade, and, secondly, for a given dyeing composition, it is not often easy to be certain of perfect reproducibility. These difficulties are increased by the fact that various side reactions change the final shade. Examples of such side reactions are the formation of compounds of the Bandrowsky base type from the oxidation bases, the recondensation of a molecule of oxidation base with certain indophenols or with certain indoanilines or indamines and the formation of quinones.

An object of the present invention is to provide a process for dyeing keratin fibers, and particularly living human hair, which does not require the addition of an oxidizing agent at the time of use. The present invention also relates to the dyes and dye compositions for use in said process.

The objects of the present invention can be achieved by using certain novel indoanilines which possess the advantage of being able to give a very particularly rich range of extremely luminous shades of excellent aesthetic quality.

It has been found that by varying the nature of the substituent in the 4'-position it is possible to change various characteristics of such dyes, in particular their solubility, affinity and compatibility. Thus, increased solubility can be achieved by introducing a hydroxyalkyl or sulphoalkyl substituent, while the solubility of the dye in an alkaline medium can be improved by introducing a mesylaminoalkyl substituent. The affinity of the dye for keratin fibers can be increased by introducing an aminoalkyl substituent.

The present invention provides a N-monoalkylamino-indoaniline of the formula (I) ##STR2## wherein

each of R₁ and R₄, which may be identical or different, represents hydrogen, halogen, lower alkyl, lower alkoxy, acylamino or ureido;

each of R₂ and R₃, which may be identical or different, represents hydrogen, halogen, lower alkyl, lower alkoxy, amino, N-(lower alkyl)-amino, N-[hydroxy-(lower alkyl)]-amino, N-[carbamyl-(lower alkyl)]-amino, acylamino or ureido;

each of R₅ or R₆, which may be identical or different, represents hydrogen, halogen, lower alkyl or lower alkoxy, with the proviso that R₅ and R₆ can occupy any two free positions but when they are both other than a hydrogen, at least one of the two occupies a meta-position relative to the --NHR₇ group; and

R₇ represents unsubstituted lower alkyl or substituted lower alkyl, and in particular hydroxy-(lower alkyl), acylamino-(lower alkyl), mesylamino-(lower alkyl), carbamyl(lower alkyl), amino-(lower alkyl), piperidino-(lower alkyl) or morpholino(lower alkyl).

By "lower" alkyl or "lower" alkoxy is meant alkyl or alkoxy containing 1 to 6, preferably 1 to 4, carbon atoms.

The invention also relates to the tautomeric form of the compounds of formula (I), especially those of the formula ##STR3## or in the case where R₃ denotes an optionally monosubstituted amino group, those of the formula ##STR4## wherein R represents hydrogen, lower alkyl, hydroxy-(lower alkyl) or carbamyl-(lower alkyl).

The compounds of this invention can be prepared by condensing a compound of the formula: ##STR5## or an addition salt thereof, on a phenolic compound of the formula ##STR6## or an addition salt thereof.

In formula (IV), Z represents --NH₂ or --NO. When Z denotes --NH₂, R₁ to R₇ are as defined above for formula (I). When Z denotes --NO, R₁ to R₆ are as defined above for formula (I) and R₇ represents unsubstituted lower alkyl.

When Z denotes --NH₂, the condensation is suitably carried out in an aqueous, aqueous-alcoholic or aqueous-acetone medium, at an alkaline pH generally greater than 8 and in the presence of an oxidizing agent, for example, ammonium persulphate, potassium ferricyanide or hydrogen peroxide. Generally the alkaline pH is obtained with ammonia or with an alkaline carbonate preferably sodium carbonate and the reaction is carried out at a temperature from 0° to 25° C.

When Z denotes --NO, the condensation is generally carried out at a temperature of about 50° C., in an aqueousethanolic medium which is neutral or has been rendered alkaline by adding a dilute solution of a base preferably sodium hydroxide.

The present invention also provides a dyeing composition for keratin fibers, and particularly for living human hair, which contains in a compatible vehicle, usually an aqueous or aqueous-alcoholic solution, at least one compound of the present invention.

These dyeing compositions generally contain 0.001 to 2% of compound of formula (I), relative to the total weight of the composition.

The dyeing composition according to this invention can contain the indoanilines of formula (I) as the only dyestuff. It is, however, possible to mix the dyestuffs of this invention with other dyestuffs usually employed for dyeing hair, for example nitrobenzene, azo, anthraquinone, indamine, indophenol and/or other indoaniline dyestuffs. Generally when a dye other than the dye of the present invention is employed, the said other dye or dyes is present in amounts of about 0.001 to 1 percent by weight of said composition.

The compositions according to the present invention are generally in the form of an aqueous or aqueous-alcoholic solution containing one or more compounds of formula (I), which may or may not be mixed with other dyestuffs. They can however also contain, for example, thickeners and be in the form of creams or gels. Suitable thickeners which can be used include cellulosic derivatives such as methyl-cellulose, hydroxyethyl-cellulose and carboxymethyl-cellulose; acrylic polymers such as the sodium salt of polyacrylic acid and ethanolamides of fatty acids, preferably mono- or diethanolamide of fatty acids of copra, carboxyvinyl polymers. The thickener can be present, for instance, in amounts of about 0.5 to 7 percent by weight of said composition.

The dyeing composition can contain, as solvents, water, lower alkanols, for example ethanol or isopropanol, and polyhydric alcohols such as glycols, for example ethylene glycol, propylene glycol, butyl glycol, diethylene glycol and the monomethyl ether of diethylene glycol. The solvent is generally present in amounts of about 1 to 60 percent by weight of said composition.

The compositions can also contain various adjuvants usually employed in cosmetics for the hair, such as wetting agents, for example oxyethylenated alkylphenols and oxyalkylenated fatty alcohol sulphates and sulphonates, dispersing agents, swelling agents, penetrating agents, softeners or perfumes. They can, moreover, be packaged in aerosol containers in the presence of a propellant gas. Suitable propellant gases include nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane or propane, or, preferably, fluorinated hydrocarbons (sold under the name of "Freon") such as dichloridifluoromethane, 1,1-difluoro-methane, 1,2,-dichloro-1,1,2,2-tetrafluoro-ethane or 1-chloro-1,1-difluoro-methane; mixtures of two or more hydrocarbons or fluorinated hydrocarbons can also be used.

The pH of the compositions, which can vary within wide limits, is generally from about 5 to 11 and preferably from 7 to 9. The pH can be adjusted by means of an alkali, for example ammonia, mono-, di- or tri-ethanolamine, di- or tri- sodium phosphate, or sodium or potassium carbonate, or by means of an acid, for example acetic acid, lactic acid, phosphoric acid or citric acid.

The dyeing of keratin fibers, particularly living human hair, by means of the dyeing compositions according to the present invention can be carried out in the usual way by applying the composition to the fibers to be dyed, leaving it in contact therewith for about 5 to 30 minutes, and then rinsing the fibers and optionally washing them and drying them.

Depending on the nature of the substituents, the indoanilines of the present invention make it possible to obtain a very wide range of colors ranging from greens to violets via blues; only yellows and oranges are not represented. The dyeings obtained are notable for their luminous nature and their rich sheen, especially a pearly or metallic sheen.

When the compositions according to the invention are in the form of aqueous-alcoholic solutions, they can also contain a cosmetic resin, in which case they form what are commonly called colored wavesetting lotions, which can be applied to wet hair before setting it in waves. These compositions generally contain about 0.001 to 0.5% of a compound of formula (I).

Representative cosmetic resins which can be used in such wavesetting lotions according to this invention include such film-forming polymers as polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester, copolymers resulting from the copolymerization of vinyl acetate and an alkyl vinyl ether, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of an acid with a long carbon chain (i.e. more than 8 carbon atoms) or an allyl or methallyl ester of an acid with a long carbon chain, copolymers resulting from the copolymerization of an ester derived from an unsaturated alcohol and from an acid with a short carbon chain (i.e. not more than 8 carbon atoms), an unsaturated acid with a short chain and at least one ester derived from a saturated alcohol with a short chain and from an unsaturated acid, and copolymers resulting from the copolymerization of at least one unsaturated ester and at least one unsaturated acid.

Representative preferred resins include polyvinylpyrrolidone having a molecular weight of 10,000 to 360,000; copolymers comprising 10% of crotonic acid and 90% of vinyl acetate having a molecular weight of 10,000 to 70,000; copolymers of vinylpyrrolidone (VP) and vinyl acetate (VA) with a molecular weight of 30,000 to 200,000, the VP/VA ratio being from 30/70 to 70/30; copolymers of maleic anhydride and methyl vinyl ether, the specific viscosity of which, measured at 25° C. as 1 g/100 ml solution in methyl ethyl ketone, is from 0.1 to 3.5 centipoises, the ethyl, isopropyl and butyl monoesters of copolymers of maleic anhydride and methyl vinyl ether; copolymers of maleic anhydride and butyl vinyl ether; terpolymers of methyl methacrylate (15-25%), stearyl methacrylate (25-35%) and dimethylaminoethyl methacrylate (52-62%), preferably quaternized, for example by means of dimethyl-sulphate, the viscosity of which, measured at the boiling point of the ether as 5% solution in dimethylformamide, is from 8 to 12 centipoises; and terpolymers of vinyl acetate (75-85%), allyl stearate (10-20%) and allyloxy-acetic acid (3-10%), the viscosity of which, measured at the boiling point of the ether as a 5% solution in dimethylformamide, is from 4.4 to 5 centipoises.

These resins are generally used in an amount from 1 to 3% by weight of the total weight of the composition.

The alcohols which are suitable for producing wavesetting lotions according to the invention are alcohols of low molecular weight, preferably ethanol or isopropanol. These alcohols are suitably employed in an amount from 20 to 70% by weight.

The wavesetting lotions according to the present invention can be employed in the usual way, by applying them to wet hair which has been washed and rinsed beforehand, constraining in a deformed state, for example by winding up on curlers and drying the hair.

The dye composition of the present invention can include a surface active agent as a carrier or as a thickening agent. Representative surface active agents that can usefully be employed include oxyethylenated alcohols, particularly oxyethylenated lauryl alcohol; partially sulfated oxyethylenated lauryl alcohol and preferably a mixture consisting of 19% lauryl alcohol oxyethylenated with 2 moles of ethylene oxide and 81% of the sodium sulfate salt of this same oxyethylenated alcohol; the alkaline or ammonium sulfate salts of long chain fatty alcohols, for example, ammonium lauryl sulfate; and oxyethylenated alkylphenols and preferably nonylphenol oxyethylenate with 4 or 9 moles of ethylene oxide per mole of alkylphenol. The surface active agent is generally employed in amounts of about 2 to 30 percent by weight of said composition.

The invention is illustrated by the following examples which are tabulated in Tables I, II, III and IV.

Examples pertaining to the preparation of the dyes of the present invention appear in Tables I and II. Table I which provides data concerning the characteristics of the prepared benzoquinoneimine dyes of this invention has columns numbered 1 through 9 inclusive. Column 1 indicates the number of the Example; Column 2 identifies the benzoquinoneimine prepared; Column 3 gives the melting point of the prepared benzoquinoneimine; Column 4 provides the empirical formula for the prepared benzoquinoneimine; and Columns 5 through 9 tabulate respectively the percentages of C, H, N, Cl and S in said dye. For each compound prepared, columns 5 through 9 carry two or three lines. The first line indicates the theoretical percentage of the indicated element corresponding to the empirical formula of column 4; line 2, and when provided, line 3 indicate the percentages found by analysis.

Table II which synopsizes the process by which the benzoquinones appearing in Table I are prepared, has eight columns numbered 1 and 10-16. Column 1 indicates, as in Table I, the number of the Example of preparation; Column 10 indicates the substituted aniline initial reactant; Column 11 identifies the substituted phenol initial reactant; Column 12 gives the molar ratio of the substituted phenol of Column 11 to the substituted aniline of Column 10; Column 13 identifies the reaction medium employed; Column 14 lists when appropriate the particular oxidizing agent used; Column 15 indicates, also when appropriate, the molar ratio of the oxidizing agent of Column 14 to phenol of Column 11; and Column 16 identifies the reaction temperature employed in degrees centigrade.

The benzoquinoneimines of Examples 1 to 8 are prepared by the reaction of a substituted nitroso aniline of the formula ##STR7## on a substituted phenol of formula (V), in ethanol or a 1:1 ethanol-water mixture made alkaline by sodium hydroxide and in the absence of an oxidizing agent.

The benzoquinoneimines of Example 9 and following are prepared by the reaction of a substituted p-phenylenediamine (substituted aniline) of the formula (VII) ##STR8## on a substituted phenol of formula (V). The molar ratio of substituted phenol:substituted aniline can be between 1:0.5 and 1:1.2 and preferably between 1:0.65 and 1:1. The molar ratio of oxidizing agent:phenol is between 1:1 and 4:1 when there is employed, as the oxidizing agent, ammonium persulfate or potassium ferricyanide. This molar ratio however is from 8:1 when there is used, as the oxidizing agent, hydrogen peroxide. The latter is generally employed in the form of a 6 weight percent solution. The reaction medium comprises water, a lower alkanol, preferably ethanol, propanol or isopropanol, an acetone-water mixture or a lower alkanol-water mixture, both generally in a 1:1 volume ratio. The pH of the reaction medium is alkalinized to a pH of at least 8, preferably by the addition thereto of an alkalizing agent such as ammonia or an alkaline carbonate.

The Examples of use include not only examples of simple dye compositions which are tabulated in Table IV, but also of dye compositions containing a cosmetic film forming resin. The latter compositions are often referred to as hair setting lotions and are tabulated in Table III.

Table III contains 12 columns numbered from 11 to 22. Column 11 indicates the number of the Example of the hair setting lotion. The column carries a number preceded by the letter M. Column 12 indicates the number of the Example of preparation according to which is prepared the benzoquinoneimine used as the dye or the letter C followed by a number which represents another dye used in admixture with the benzoquinoneimine. The name of this additional dye appears at the bottom of the table. Column 13 indicates the amount of dye expressed in weight percent of the total weight of the composition. Columns 14-17 concern the cosmetic resin used. Column 14 indicates the name of the resin and column 15 its average molecular weight. Column 16 reports the viscosity of the resin in centipoises while Column 17 indicates the weight percent of the resin relative to the total weight of the composition. Columns 18 and 19 reveal, respectively, the name and the weight percent (relative to the total weight of the composition), of the alcohol used. Column 20 indicates the pH of the composition while Column 22 indicates the color obtained on the bleached hair (D) or 95% naturally white hair (B 95). This latter indication of the type of hair to which the composition is applied appears in column 21. In Column 14, the name of the resin, polymer or copolymer, is indicated by abbreviations. These abbreviations and their meaning are as follows: PVP=polyvinylpyrrolidone; VA/CA=copolymer of vinyl acetate and crotonic acid; VP/VA=copolymer of vinylpyrrolidone and vinyl acetate; and MM/StM/DEM=copolymer of methyl methacrylate (15-25%)/stearyl methacrylate (25-35%)/dimethylaminoethyl methacrylate (52-62%) quaternized with dimethyl sulfate.

The viscosity of the VP/VA copolymer is measured at 25° C. in a 5% solution in ethanol. The viscosity of the terpolymer MM/StM/DEM is measured at the boiling point of ether (35° C.) and at a concentration of 5% in dimethylformamide.

Table IV carries 12 columns numbered from 31 to 42. Column 31 indicates the number of the Example of the dye composition. This column carries a number preceded by the letter T. Column 32 indicates the number of the Example of preparation according to which is prepared the benzoquinoneimine used as the dye or the letter C followed by a number which represents another dye used in admixture with the benzoquinoneimine and for which the name appears at the bottom of the Table. Columns 34 and 35 indicate respectively the nature and the weight percent of the surface active agent used. Column 33 indicates the amount of dye employed, expressed in weight percent. Columns 36 and 37 indicate, respectively, the name and weight percent of the solvent used while Columns 38 and 39 indicate the name and weight percent of the adjuvant used. Column 40 indicates the pH of the composition and Column 42 indicates the color obtained on bleached hair (D) or on 95% naturally white hair (B 95). This latter indication of the type of hair to which the composition is applied appears in Column 41. All percents indicated are by weight of the total weight of the composition.

In Columns 34 and 38, the name of the surface active agent and various adjuvants are indicated by abbreviations, the meanings of which appear at the bottom of the Table.

    TABLE I       ANALYSIS Example  Melting  C H N Cl S N° BENZOQUINONEIMINE Point      Empirical Formula % % % % % (1) (2) (°C.)(3) (4) (5) (6) (7) (8)      (9)        1 N--[(4'-ethylamino)phenyl]-2-methyl-5- 225 C.sub.17 H.sub.20 N.sub.4      O.sub.2 65.36  6.45  17.94       carbamylmethylamino benzoquinoneimine      65.06  6.59  18.16               65.08  6.64  18.04 2 N--[(4'-ethylamino-      2'-methyl)phenyl]-2,6- 128 C.sub.17 H.sub.21 N.sub.3 O 72.05  7.47      14.83  dimethyl-3-amino benzoquinoneimine   72.38  7.62  15.12          72.45  7.51  15.09 3 N--[(4'-ethylamino-2'-methyl)phenyl]-2- 182      C.sub.16 H.sub.19 N.sub.3       O 71.34  7.11  15.60  methyl-5-amino benzoquinoneimine   71.41  7.21      15.76               71.32  7.32  15.82 4 N--[(4'-ethylamino)phenyl]-2-chl      oro-5-amino 184 C.sub.14 H.sub.14 N.sub.3 OCl 60.98  5.09  15.25  12.87      benzoquinoneimine   61.07  5.17  15.24  12.92                 60.94      5.14  15.34  13.90 5 N--[(4'-ethylamino-3'-methyl)phenyl]-2,6- 147      C.sub.17 H.sub.21 N.sub.3 O 72.05  7.47  14.83  dimethyl-3-amino      benzoquinoneimine   71.78  7.42  15.04               71.67  7.53  14.65      6 N--[4'-ethylamino)phenyl]-2,6-dimethyl-3- 162 C.sub.16 H.sub.19      N.sub.3 O 71.34  7.11  15.60  amino benzoquinoneimine   71.12  7.11      15.79               71.28  6.90  15.76 7 N--[(4'-methylamino-2',5'-dimeth      yl)phenyl]- 210 C.sub.17 H.sub.21 N.sub.3       O 72.05  7.47  14.83  2,6-dimethyl-3-amino benzoquinoneimine   71.94      7.77  14.81 8 N--[(4'-methylamino)phenyl]-2-methyl-5-amino 162 C.sub.14      H.sub.15 N.sub.3 O 69.69  6.27  17.42  benzoquinoneimine   68.52  6.33      17.62               68.57  6.39  17.55 9 N--[(4'-methylamino-3'-methoxy)p      henyl]-2,6- 156 C.sub.16 H.sub.18 N.sub.2 O.sub.2 71.09  6.71  10.36      dimethyl benzoquinoneimine   70.86  6.83  10.42               70.79      6.76  10.49 10 N--[(4'-methylamino)phenyl]-2,6-dimethyl-3- 166 C.sub.15      H.sub.17 N.sub.3 O 70.56  6.71  16.46  amino benzoquinoneimine   70.75      6.67  16.49              MW = 255 (1) 70.41  6.68  16.52    251 (2) 11      N--[(4'-ethylamino-2'-methyl)phenyl]-3-chloro 222 C.sub.16 H.sub.17      N.sub.4 O.sub.2 Cl 57.74  5.11  16.87  10.67  6-ureido benzoquinoneimine        57.26  5.04  16.61  10.41                 57.30  5.21  16.71  10.47 12      N--[(4'-butylamino-3'-chloro)phenyl]-2-methyl 87 C.sub.19 H.sub.22      N.sub.3 O.sub.2       Cl 63.42  6.16  11.67  9.85  5-acetylamino benzoquinoneimine   63.06      6.16  11.87  9.69                 63.14  6.23  11.73  9.66 13 N--[(4'-eth      ylamino-2'-methyl)phenyl]-3-ureido 212 C.sub.16 H.sub.18 N.sub.4 O.sub.2      64.41  6.08  18.78  benzoquinoneimine   64.29  6.25  18.47      64.58  6.09  18.62 14 N--[(4'-methylamino)phenyl]-2,6-dimethyl 158      C.sub.17 H.sub.19 N.sub.3 O.sub.2 68.66  6.44  14.13  3-acetylamino      benzoquinoneimine   68.29  6.57  14.25               68.32  6.58  14.34      15 N--[(4'-ethylamino-2'-methyl)phenyl]-3-chloro 162 C.sub.17 H.sub.18      N.sub.3 O.sub.2       Cl 61.54  5.43  12.67  10.71  6-acetylamino benzoquinoneimine   60.98      5.26  12.97  10.39                 61.22  5.25  12.86  10.45 16 N--[(4'-e      thylamino)phenyl]-2-methyl-5-acetyl- 100 C.sub.17 H.sub.19 N.sub.3      O.sub.2 68.66  6.44  14.13  amino benzoquinoneimine   68.12  6.44  13.98                    68.41  6.66  13.94      (1) Molecular weight  calculated      (2) Molecular weight determined by potentiometric titration in acetic aci      using perchloric acid     17 N--[(4'-butylamino-3'-chloro)phenyl] 124 C.sub.18 H.sub.20 N.sub.3      O.sub.2 Cl 62.52  5.80  12.15  10.25     3-acetylamino benzoquinoneimine        62.35  6.03  12.21  10.40                 62.29  6.04  12.09  10.17 18      N--[(4'-ethylamino)phenyl]-2-chloro-5-acetyl- 198 C.sub.16 H.sub.16      N.sub.3 O.sub.2 Cl 60.47  5.04  13.22  amino benzoquinoneimine   59.98      4.97  13.21               59.85  5.06  13.17 19 N-[(4'-ethylamino-3'chlor      o)phenyl] 144 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl 61.53  5.46  12.66      10.68  2-methyl-5-acetylamino benzoquinoneimine   61.57  5.61  12.53      10.79                 61.28  5.51  12.86  10.65 20 N--[4'-(β-acetyla      mino-ethyl)amino phenyl] 126 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl 61.54      5.46  12.64  10.70  3-methyl-6-chloro benzoquinoneimine   61.24  5.60      12.55  10.59                 61.32  5.54  12.47  10.48 21 N--[(4'-(β      -hydroxyethyl)amino phenyl] 206 C.sub.14 H.sub.14 N.sub.3 O.sub.2  50.00       4.16  12.50  23.84  2-bromo-5-amino benzoquinoneimine   50.12  4.35      12.60  23.62                50.24  4.28  12.36  23.65 22 N--[(4'-β-h      ydroxyethylamino-3'-methyl)phenyl] 242 C.sub.18 H.sub.21 N.sub.3 O.sub.3      66.03  6.47  12.84  2-methyl-5-acetylamino benzoquinoneimine   65.85      6.65  12.93               65.87  6.44  13.06 23 N--[(4'-β-morpholino      ethylamino)phenyl]-2-chloro 180 C.sub.20 H.sub.23 N.sub.4 O.sub.3 Cl      59.62  5.71  13.91  8.81  5-acetylamino benzoquinoneimine   59.03  5.61      14.06  8.72                 58.98  5.87  14.18  8.74 24 N--[(4'-β-mo      rpholinoethylamino)phenyl]-3-ureido 178 C.sub.19 H.sub.23 N.sub.5      O.sub.3 61.77  6.28  18.96  benzoquinoneimine   61.05  6.26  18.82              61.28  6.22  18.75 25 N--[(4'-β-mesylamino-ethylamino)phenyl      ]-2- 126 C.sub.18 H.sub.22 N.sub.4 O.sub.4 S 55.38  5.68  14.35      methyl-5-acetylamino benzoquinoneimine   55.02  5.97  14.35      55.17  5.82  14.43 26 N--[(4'-β-acetylaminoethylamino)phenyl]-3-      230 C.sub.17 H.sub.18 N.sub.5 O.sub.3       Cl 54.33  4.80  18.64  chloro-6-ureido benzoquinoneimine   54.22  5.11      18.67               54.48  5.08  18.55 27 N--[(4'-β-hydroxyethylamin      o-3'-methoxy)phenyl] 150 C.sub.16 H.sub.19 N.sub.3 O.sub.3 63.77  6.36      13.95  2-methyl-5-amino benzoquinoneimine   63.81  6.53  14.02          64.02  6.65  14.19 28 N--[(4'-β-mesylaminoethylamino-3'-methyl)      148 C.sub.20 H.sub.26 N.sub.4 O.sub.4 S 57.40  6.26  13.39    7.64      phenyl]-2,6-dimethyl-5-acetylamino benzoqui-   57.52  6.24  13.53      7.66  noneimine                 57.23  6.27  13.45    7.44 29 N--[(4'-.be      ta.-acetylaminoethylamino-3'-methoxy) 183 C.sub.19 H.sub.24 N.sub.4      O.sub.3 64.02  6.79  15.72  phenyl]-2,6-dimethyl-5-amino benzoquinonei-       63.87  6.58  15.51  mine             63.74  6.70  15.20 30 N--[(4'-.beta      .-mesylamino ethylamino-3'-chloro) 244 C.sub.18 H.sub.21 N.sub.4 O.sub.4      S Cl 50.88  4.98  13.18    7.54  phenyl]-2-methyl-5-acetylamino benzoquin      onei-   50.71  5.20  13.36    7.26  mine                 50.77  5.20      13.42    7.38 31 N--[(4'-β-acetylamino-3'-chloro)phenyl]2,6- 161      C.sub.18 H.sub.20 N.sub.3 O.sub.2 Cl 62.51  5.79  12.15  10.27  dimethyl      benzoquinoneimine   62.29  5.80  12.21  10.23                 62.36      5.94  12.10  10.38 32 N--[(4'-β-hydroxyethylamino-3'-methoxy)phenyl]      - 165 C.sub.17 H.sub.21 O.sub.3       N.sub.3 64.74  6.71  13.33  2,6-dimethyl-5-amino benzoquinoneimine      64.66  6.78  13.17               64.50  6.78  13.15 33 N--[(4'-β-hyd      roxyethylamino-3'-methoxy)phenyl]- 110 C.sub.19 H.sub.23 O.sub.4      N.sub.3.H.sub.2 O 60.79  6.71  11.19  2,6-dimethyl-5-acetylamino      benzoquinoneimine   60.53  6.58  11.31               60.45  6.61  11.36      34 N--[(4'-β-hydroxyethylamino-3'-chloro)phenyl]- 144 C.sub.16      H.sub.15 N.sub.3 O.sub.3       Cl.sub.2 52.19  4.10  11.41  19.26  3-chloro-6-acetylamino benzoquinonei      mine   52.05  4.42  11.52  19.16                 51.93  4.38  11.36      19.23 35 N--[(4'-β-aminoethylamino-3'-methyl-6'-methoxy) 168      C.sub.18 H.sub.24 N.sub.4       O.sub.2 65.83  7.37  17.06  phenyl]-2,6-dimethyl-3-amino benzoquinoneimi      ne   65.12  7.03  16.98               65.24  7.17  16.84 36 N--[(4'-.beta      .-mesylaminoethylamino-3'-methyl) 242 C.sub.19 H.sub.24 N.sub.4 O.sub.4      S 56.43  5.98  13.86    7.91  phenyl]-2-methyl-5-acetylamino benzoquinone      i-   56.41  6.04  14.07    7.74  mine                 56.58  6.21  14.12         7.84 37 N--[(4'-β-acetylaminoethylamino-3'-methyl) 222 C.sub.18      H.sub.21 N.sub.5       O.sub.3 60.83  5.96  19.71  phenyl]-3-ureido benzoquinoneimine   60.66      6.16  19.61               60.57  5.97  19.70 38 N--[(4'-β-carbamylme      thylamino-3'-methyl) 240 C.sub.19 H.sub.22 N.sub.4 O.sub.3 64.39  6.26      15.81  phenyl]-2,6-dimethyl-3-acetylamino benzo-   64.98  6.47  15.45      quinoneimine             64.87  6.53  15.78 39 N--[(4'-γ-morpholino      propylamino-3'-chloro) 214 C.sub.21 H.sub.24 N.sub.4 O.sub.3 Cl.sub.2      55.87  5.36  12.41  15.74  phenyl]-3-chloro-6-acetylamino benzoquinonei-        55.58  5.56  12.56  15.78  mine  MW 451 (1)    448 (2) 40 N--[      (4'-methylamino)phenyl]-2,6-dimethyl benzo- 132 C.sub.15 H.sub.16      N.sub.2 O 74.97  6.71  11.66  quinoneimine   74.68  6.91  11.44    MW      240 (1)    239 (2) 41 N--[(4'-methylamino-3'-methyl)phenyl]-2,6-di- 160      C.sub.18 H.sub.21 N.sub.3       O.sub.2 69.43  6.80  13.50  methyl-3-acetylamino benzoquinoneimine      69.36  6.73  13.28 42 N--[(4'-methylamino-2'-methyl)phenyl]-2,6-di- 218      C.sub.18 H.sub.21 N.sub.3       O.sub.2 69.43  6.80  13.50  methyl-3-acetylamino benzoquinoneimine      69.60  6.68  13.27 43 N--[(4'-methylamino-3'-methyl)phenyl]-2,6-di- 138      C.sub.16 H.sub.18 N.sub.2 O 75.56  7.13  11.02  methyl benzoquinoneimine        75.69  7.12  11.11 44 N--[(4'-methylamino-2'-methyl)phenyl]-2,6- 129.5      C.sub.16 H.sub.18 N.sub.2       O 75.56  7.13  11.02  dimethyl benzoquinoneimine   75.61  7.01  11.32       MW 254 (1)    260 (2) 45 N--[(4'-β-hydroxyethylamino-2'-methoxy)phe      nyl]- 163 C.sub.18 H.sub.21 N.sub.3       O.sub.4 62.96  6.16  12.24  2-methyl-5-acetylamino benzoquinoneimine      62.76  6.31  12.24 46 N--[(4'-β-acetylaminoethylamino-3'-chloro)      156 C.sub.17 H.sub.18 N.sub.3 O.sub.3       Cl 58.70  5.18  12.08  phenyl]-3-methoxy benzoquinoneimine   58.41      4.97  12.20               58.56  5.04  12.17 47 N--[(4'-β-mesylamino      ethylamino)phenyl]-2,6-di- 157 C.sub.19 H.sub.24 N.sub.4 O.sub.4 S 56.43       5.98  13.86    8.07  methyl-3-acetylamino benzoquinoneimine   56.30      6.00  13.98    7.91 48 N--[(4'-β-hydroxyethylamino)phenyl]-2-methyl-      5- 162 C.sub.17 H.sub.19 N.sub.3 O.sub.3 65.16  6.11  13.41  acetylamino      benzoquinoneimine   65.16  6.25  13.63 49 N--[(4'-β-hydroxyethylamin      o-3'-methoxy)phenyl]- 166 C.sub.17 H.sub.20 N.sub.2 O.sub.3 67.98  6.71      9.33  2,6-dimethyl benzoquinoneimine   67.90  6.72  9.30 50 N--[(4'-.gamm      a.-morpholinopropylamino-3'-chloro) 212 C.sub.19 H.sub.22 N.sub.4      Br.sub.2       ClO.sub.2 50.17  4.85  12.35  phenyl]-2-bromo-5-amino benzoquinoneimine        50.10  5.06  12.65 51 N--[ (4'-methylamino-2'-methoxy)phenyl]-2,6-di-      249 C.sub.18 H.sub.21 N.sub.3       O.sub.3 66.03  6.47  12.84  methyl-5-acetylamino benzoquinoneimine      65.84  6.52  12.79 52 N--[(4'-methylamino-2'-methoxy)phenyl]-2-methyl      204 C.sub.17 H.sub.19 N.sub.3 O.sub.3 65.16  6.11  13.41  5-acetylamino      benzoquinoneimine   64.92  6.19  13.34 53 N--[(4'-methylamino-3'-methoxy)      phenyl]-2,6-di- 195 C.sub.16 H.sub.19 N.sub.3 O.sub.2 67.34  6.71  14.73       methyl-5-amino benzoquinoneimine   67.20  6.71  14.99 54 N--[(4'-methyla      mino-2'-methoxy)phenyl]-2- 178 C.sub.15 H.sub.17 N.sub.3       O.sub.2.0.5H.sub.2       O 64.28  6.42  15.00  methyl-5-amino benzoquinoneimine   64.26  6.61      14.87 55 N--[(4'-methylamino-3'-chloro)phenyl]-2-methyl- 206 C.sub.16      H.sub.16 Cl N.sub.3       O.sub.2 60.45  5.07  13.22  5-acetylamino benzoquinoneimine   60.35      5.23  13.31 56 N--[(4'-methylamino-3'-chloro)phenyl]-2,6- 166 C.sub.17      H.sub.18 Cl N.sub.3       O.sub.2 61.53  5.47  12.66  10.68  dimethyl-5-acetylamino benzoquinoneim      ine   61.61  5.62  12.51  10.53 57 N--[(4'-methylamino-3'-chloro)phenyl]-      2,6-di- 127 C.sub.15 H.sub.15 Cl N.sub.2 O 65.58  5.50  10.19  12.90      methyl benzoquinoneimine   65.41  5.60  10.24  12.90 58 N--[(4'-methylami      no-3'-chloro)phenyl]-2,6- 165 C.sub.15 H.sub.16 Cl N.sub.3 O.0.5H.sub.2      O 60.30  5.70  14.01  11.91  dimethyl-5-amino benzoquinoneimine   60.64      5.70  14.07  11.98 59 N--[(4'-methylamino-3'-chloro)phenyl]-2-methyl-      174 C.sub.14 H.sub.14 Cl N.sub.3 O 60.98  5.11  15.24  12.86  5-amino      benzoquinoneimine   61.17  5.32  15.10  12.67 60 N--[(4'-methylamino-2'-c      hloro)phenyl]-2,6- 235 C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2 61.53  5.47      12.66  10.68  dimethyl-5-acetylamino benzoquinoneimine   61.26  5.56      12.90  10.47 61 N--[(4'-methylamino-2'-chloro)phenyl]-2,6-di- 182      C.sub.15 H.sub.16 N.sub.3 OCl 62.16  5.56  14.50  12.23  methyl-5-amino      benzoquinoneimine   61.92  5.71  14.30  12.05 62 N--[(4'-methylamino-2'-c      hloro)phenyl]-2-methyl- 180 C.sub.14 H.sub.14 N.sub.3 O Cl 60.98  5.11      15.24  12.86  5-amino benzoquinoneimine   60.83  4.99  15.10  12.74 63      N--[(4'-methylamino-2'-chloro)phenyl]-2- 234 C.sub.16 H.sub.16 N.sub.3      O.sub.2 Cl 60.47  5.07  13.22  methyl-5-acetylamino benzoquinoneimine      60.42  5.29  13.18 64 N--[(4'-methylamino-3'-methoxy)phenyl]-2,6- 120      C.sub.18 H.sub.21 N.sub.3 O.0.5H.sub.2       O 64.28  6.54  12.50  dimethyl-5-acetylamino benzoquinoneimine 158(1)      64.52  6.78  12.69 65 N--[(4'-methylamino-2'-chloro)phenyl]-2-methyl-      190 C.sub.16 H.sub.18 N.sub.3 O.sub.2 Cl 60.09  5.67  13.14  11.11      5-β-hydroxyethylamino benzoquinoneimine   60.15  5.86  13.31  11.19      66 N--[(4'-methylamino-2'-methoxy)phenyl]-2,6-di- 152 C.sub.16 H.sub.18      N.sub.2 O.sub.2 71.09  6.71  10.36  methyl benzoquinoneimine   71.40      6.91  10.15 67 N--[(4'-methylamino-2'-methoxy)phenyl]-2,6-di- 200      C.sub.16 H.sub.19 N.sub.3 O.sub.2 67.34  6.71  14.73  methyl-5-amino      benzoquinoneimine   67.25  6.57  14.77 68 N--[(4'-methylamino-2'-methyl)p      henyl]2-methyl- 140 C.sub.15 H.sub.17 N.sub.3 O.0.5H.sub.2 O 68.16  6.86       15.90  5-amino benzoquinoneimine   68.35  6.99  16.11 69 N-- [(4'-methyl      amino-2'-methyl)phenyl]-2,6-di- 149 C.sub.16 H.sub.19 N.sub.3 O 71.34      7.11  15.60  methyl-5-amino benzoquinoneimine   71.30  7.03  15.59 70      N--[(4'-methylamino-2'-chloro)phenyl]-2,6-di- 138 C.sub.15 H.sub.15      N.sub.2 O Cl 65.57  5.50  10.20  12.91  methyl benzoquinoneimine   65.56       5.74  10.35  12.76 71 N--[(4'-methylamino-2'-methyl)phenyl]-2-methyl-      175 C.sub.17 H.sub.19 N.sub.3 O.sub.2 68.66  6.44  14.13  5-acetylamino      benzoquinoneimine   68.66  6.63  14.35 72 N--[(4'-methylamino-3'-methyl)p      henyl]-2,6-di- 152 C.sub.16 H.sub.19 N.sub.3 O 71.34  7.11  15.60      methyl-5-amino benzoquinoneimine   71.20  7.01  15.73 73 N--[(4'-methylam      ino-3'-methyl)phenyl]-2-methyl- 210 C.sub.17 H.sub.19 N.sub.3 O.sub.2      68.66  6.44  14.13  5-acetylamino benzoquinoneimine   68.64  6.49  14.28      74 N--[(4'-methylamino-3'-methyl)phenyl]-2-methyl- 166 C.sub.15 H.sub.17      N.sub.3 O 70.56  6.71  16.46  5-amino benzoquinoneimine   70.33  6.72      16.34 75 N--[(4'-methylamino)phenyl]-2-methyl-5-acetyl- 161 C.sub.16      H.sub.17 N.sub.3 O.sub.2 67.82  6.05  14.83  amino benzoquinoneimine      67.72  6.18  14.92 76 N--[(4'-methylamino-3'-methoxy)phenyl]-2- 179      C.sub.18 H.sub.21 N.sub.3       O.sub.4 62.96  6.16  12.24  methyl-5-carbethoxyamino benzoquinoneimine       63.02  6.28  12.06 77 N--[(4'-methylamino-3'-chloro)phenyl]-2-methyl-      228 C.sub.15 H.sub.15 N.sub.4 O.sub.2 Cl 56.51  4.71  17.58  11.14      5-ureido benzoquinoneimine   56.61  4.90  17.63  10.93 78 N--[(4'-β-      hydroxyethylamino-3'-chloro)phenyl]- 195 C.sub.17 H.sub.19 N.sub.4      O.sub.3       Cl 56.30  5.24  15.42  9.79  2,6-dimethyl-3-ureido benzoquinoneimine      56.41  5.34  15.33  9.81 79 N--[(4'-β-hydroxyethylamino-3'-chloro)ph      enyl]- 280 C.sub.15 H.sub.15 N.sub.4 O.sub.3 Cl 53.81  4.48  16.74      10.61  3-ureido benzoquinoneimine   53.86  4.71  16.62  10.36 80      N--[(4'-β-hydroxyethylamino-3'-chloro)phenyl]- 178 C.sub.16      H.sub.16 N.sub.3 O.sub.3 Cl 57.57  4.79  12.59  10.64  3-acetylamino      benzoquinoneimine   57.39  4.79  12.71  10.48 81 N--[(4'-β-hydroxyet      hylamino-3'-chloro)phenyl]- 176 C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl      58.70  5.18  12.08  10.21  2-methyl-5-acetylamino benzoquinoneimine      58.83  5.19  12.17  10.36 82 N--[(4'-β-hydroxyethylamino-3'-chloro)p      henyl]- 240 C.sub.16 H.sub.17 N.sub.4 O.sub.3 Cl 55.09  4.88  16.07      10.18  2-methyl-5-ureido benzoquinoneimine   54.84  4.97  16.03  10.18                    54.83  4.91  16.00  10.30 83 N--[(4'-methylamino)phenyl]-2-      methyl-5- 228 C.sub.16 H.sub.18 N.sub.4 O.sub.2 --H.sub.2 O     17.71      carbamylmethylamino benzoquinoneimine                 17.40    MW 298      (1)    304 (2) 84 N--[(4'-methylamino-2'-methyl)phenyl]- 200 C.sub.17      H.sub.20 N.sub.4 O.sub.2     17.94  2-methyl-5-carbamylmethylamino      benzoquinonei-       17.58   mine       17.68 85 N--[(4'-methylamino-3'-m      ethyl)phenyl] -2-methyl- 240 C.sub.17 H.sub.20 N.sub.4 O.sub.2 65.36      6.45  17.94  5-carbamylmethylamino benzoquinoneimine   65.18  6.60      18.10 86 N--[(4'-β-acetylaminoethylamino-3'chloro) 230 with      C.sub.19 H.sub.22 N.sub.5 O.sub.3       Cl 56.50  5.45  17.35  phenyl]-2-methyl-5-carbamylmethylamino benzo-      decomposi-  56.20  5.53  17.45  quinoneimine tion 87 N--[(4'-β-mesyl      aminoethylamino-3'-chloro) 203 with C.sub.18 H.sub.22 N.sub.5 O.sub.4      SCl.H.sub.2       O 47.21  5.28  15.30  7.74  6.99  phenyl]-2-methyl-5-carbamylmethylamino      - decomposi-  47.34  5.15  14.98  7.78  7.03  benzoquinoneimine tion 88      N--[(4'-β-hydroxyethylamino)phenyl]-2-methyl 235 with C.sub.17      H.sub.20 N.sub.4 O.sub.3.H.sub.2       O 58.94  6.40  16.18  5-carbamylmethylamino benzoquinoneimine decomposi-        59.15  6.26  16.33   tion 89 N--[(4'-β-mesylaminoethylamino-3'-met      hyl) 215 with C.sub.19 H.sub.25 N.sub.5 O.sub.4 S 54.40  6.01  16.70      phenyl]-2-methyl-5-carbamylmethylamino decomposi-  54.26  5.90  16.57      benzoquinoneimine tion 90 N--[(4'-methylamino-3'chloro)phenyl]-2-methyl-      120 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl.H.sub.2 O 54.78  5.46  16.26      10.11 5-carbamylmethylamino benzoquinoneimine 212(3)  54.67  5.16  16.53      10.13 91 N--[(4'-β-mesylaminoethylamino-3'-chloro) 228 C.sub.17      H.sub.20 N.sub.5 O.sub.4       SCl 47.94  4.70  16.45  8.34  7.50  phenyl]-2-methyl-5-ureido benzoquino      neimine   47.78  4.74  16.63  8.54  7.52           8.47  7.56 92      N--[(4'-β-mesylaminoethylamino-3'-chloro) 253 C.sub.16 H.sub.18      N.sub.5 O.sub.4 SCl       8.62  7.72  phenyl]-3-ureido benzoquinoneimine              8.70  7.94          8.79 93 N--[(4'-methylamino-3'-chloro)phenyl]      -3-acetyl-198 C.sub.15 H.sub.14 N.sub.3 O.sub.2 Cl 59.31  4.61  13.84      amino benzoquinoneimine   59.21  4.81  13.93 94 N--[4'-ethylamino-3'-meth      yl)phenyl]-2-methyl- 185 C.sub.18 H.sub.21 N.sub.3 O.sub.2 69.45  6.75      13.50  5-acetylamino benzoquinoneimine   69.20  7.00  13.74 95 N--[(4'-.b      eta.-hydroxyethylamino-3'-chloro)phenyl]- 98 C.sub.18 H.sub.20 N.sub.3      O.sub.3       Cl 59.75  5.53  11.61  2,6-dimethyl-3-acetylamino benzoquinoneimine      59.44  5.77  11.61 96 N--[(4'-methylamino-3'-chloro)phenyl]-2,6- 218      C.sub.16 H.sub.17 N.sub.4 O.sub.2       Cl 57.74  5.11  16.84  dimethyl-3-ureido benzoquinoneimine   57.77      5.45  16.90 97 N--[(4'-β-hydroxyethylamino-3'-chloro)phenyl] 170      C.sub.17 H.sub.19 N.sub.4 O.sub.3 Cl.H.sub.2 O 53.63  5.51  14.71      2-methyl-5-carbamylmethylamino benzoquinonei-   53.65  5.38  14.94  mine      98 N--[(4'-mesylaminoethylamino-3'-chloro)phenyl]- 230 C.sub.17 H.sub.19      N.sub.4 O.sub.4       S Cl 49.69  4.63  13.64    7.80  3-acetylamino benzoquinoneimine      49.95  4.82  13.54    7.76 99 N--[(4'-methylamino-3'-chloro)phenyl]-3-ure      ido 258 C.sub.14 H.sub.13 N.sub.4 O.sub.2 Cl 55.17  4.27  18.39  11.66      benzoquinoneimine   55.14  4.56  18.64  11.57      (1) molecular weight calculated      (2) molecular weight determined by potentiometric titration in acetic aci      using perchloric acid      (3) double melting point

                                      TABLE II                                     __________________________________________________________________________     Ex-                                    Reaction           Reaction             am-                               Molar                                                                               Medium        Molar                                                                               Temp-                ple                               Ratio                                                                               (13)    Oxidizing                                                                            Ratio                                                                               erature              No ANILINE (Substituted)  PHENOL  (11):(10)                                                                           1:1     Agent (14):(11)                                                                           (C.°)         (1)                                                                               (10)                   (11)    (12) vol ratio                                                                              (14)  (15) (16)                 __________________________________________________________________________      1 4-nitroso-N--ethylaniline hydrochloride                                                               2-methyl-5-                                                                            1:1  Ethanol-water      50°                                     carbamyl-                                                                      methylamino                                                                    phenol                                                2 3-methyl-4-nitroso-N--ethylaniline                                                                    2,6-dimeth-                                                                            1:1  "                  45°                                     yl-3-amino                                                                     phenol hy-                                                                     drochloride                                           3   "                    2-methyl-5-                                                                            1:1  "                  50°                                     amino phenol                                          4 4-nitroso-N--ethylaniline hydrochloride                                                               2-chloro-5-                                                                            1:1  "                  40°                                     amino phenol                                          5 2-methyl-4-nitroso-N--ethylaniline                                                                    2,6-dimeth-                                                                            1:1  "                  40°                                     yl-3-amino                                                                     phenol hy-                                                                     drochloride                                           6 4-nitroso N--ethylaniline hydrochloride                                                               2,6-dimeth-                                                                            1:1  "                  40°                                     yl-3-amino                                                                     phenol hy-                                                                     drochloride                                           7 2,5-dimethyl-4-nitroso-N--methylaniline                                                               2,6-dimeth-                                                                            1:1  "                  50-60°           hydrochloride          yl-3-amino                                                                     phenol hy-                                                                     drochloride                                           8 4-nitroso-N--methylaniline                                                                            2-methyl-5-                                                                            1:1  "                  45°                                     amino phenol                                          9 2-methoxy-4-amino-N--methylaniline sulfate                                                            2,6-dimeth-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                                              yl phenol            persulfate                      10 N--methyl paraphenylenediamine dihydro-                                                               2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             1:1  0                       chloride               yl-3-amino           sulfate                                                   phenol hy-                                                                     drochloride                                          11 3-methyl-4-amino-N--ethylaniline dihydro-                                                             3-chloro-6-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             1:1  0                       chloride               ureido       water   persulfate                                                phenol                                               12 2-chloro-4-amino-N--butylaniline sulfate                                                              2-methyl-5-                                                                            1:1  acetone-water                                                                          Ammonium                                                                             1:1  3                                              acetylamino          persulfate                                                phenol                                               13 3-methyl-4-amino-N--ethylaniline dihydro-                                                             3-ureido                                                                               1:1  "       Ammonium                                                                             1:1  0                       chloride               phenol               persulfate                      14 N--methyl paraphenylenediamine dihydro-                                                               2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             1:1  0                       chloride               yl-3-ace-            persulfate                                                tylamino                                                                       phenol                                               15 3-methyl-4-amino-N--ethylaniline dihydro-                                                             3-chloro-6-                                                                            1:1  "       Ammonium                                                                             2:1  0                       chloride               acetylamino          persulfate                                                phenol                                               16 N--ethyl paraphenylenediamine dihydro-                                                                2-methyl-5-                                                                            1:1  "       Ammonium                                                                             1:1  0                       chloride               acetylamino          persulfate                                                phenol                                               17 2-chloro-4-amino-N--butylaniline sulfate                                                              3-acetyl-                                                                              1:1  "       Ammonium                                                                             1:1  0                                              amino phenol         persulfate                      18 N--ethyl paraphenylenediamine dihydro-                                                                2-chloro-5-                                                                            1:1  water   Ammonium                                                                             2:1  0                       chloride               acetylamino          persulfate                                                phenol                                               19 2-chloro-4-amino-N--ethylaniline sulfate                                                              2-methyl-5-                                                                            1:1  acetone-water                                                                          Ammonium                                                                             1:1  0                                              acetylamino          persulfate                                                phenol                                               20 4-amino-N--(β-acetylamino) ethylaniline                                                          3-methyl-6-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0                       sulfate                chloro phenol                                                                               water   persulfate                      21 4-amino-N--(β-hydroxyethyl) aniline                                                              2-bromo-5-                                                                             1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0                       sulfate                amino phenol water   persulfate                      22 2-methyl-4-amino-N--(β-hydroxyethyl)                                                             2-methyl-5-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                       aniline sulfate        acetylamino          persulfate                                                phenol                                               23 4-amino-N--(β-morpholinoethyl) aniline                                                           2-chloro-5-                                                                            1:1  "       Ammonium                                                                             2:1  0                                              acetylamino          persulfate                                                phenol                                               24 4-amino-N--(β-morpholinoethyl) aniline                                                           3-ureido                                                                               1:1  Isopropanol-                                                                           Potassium                                                                            4:1  0                                              phenol       water   ferricyanide                    25 4-amino-N--(β-mesylaminoethyl) aniline                                                           2-methyl-5-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0                       sulfate                acetylamino  water   persulfate                                                phenol                                               26 4-amino-N--(β-acetylaminoethyl) aniline                                                          3-chloro-6-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0                       sulfate                ureido phenol                                                                               water   persulfate                      27 2-methoxy-4-amino-N--(β-hydroxyethyl)                                                            2-methyl-5-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             1:1  +5                      aniline sulfate        amino phenol water   persulfate                      28 2-methyl-4-amino-N-- (β-mesylaminoethyl)                                                         2,6-dimetnyl-                                                                          1:1  Acetone-water                                                                          Ammonium                                                                             1:1  0                       aniline sulfate        5-acetylamino        persulfate                                                phenol                                               29 2-methoxy-4-amino-N--(β-acetylaminoethyl)                                                        2,6-dimethyl                                                                           1:1  Water   Ammonium                                                                             1:1  0                       aniline sulfate        5-amino              persulfate                                                phenol                                                                         hydrochloride                                        30 2-chloro-4-amino-N--(β-mesylaminoethyl)                                                          2-methyl-5-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                       aniline sulfate        acetylamino          persulfate                                                phenol                                               31 2-chloro-4-amino-N--(β-acetylaminoethyl)                                                         2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             2:1  0                       aniline sulfate        yl phenol            persulfate                      32 2-methoxy-4-amino-N--(β-hydroxyethyl)                                                            2,6-dimeth-                                                                            1:1  Water   Ammonium                                                                             2:1  0                       aniline sulfate        yl-5-amino           persulfate                                                phenol hy-                                                                     drochloride                                          33 2-methoxy-4-amino-N--(β-hydroxyethyl)                                                            2,6-dimeth-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             1.1:1                                                                               0                       aniline sulfate        yl-5-acetyl-         persulfate                                                amino phenol                                         34 2-chloro-4-amino-N--(β-hydroxyethyl)                                                             3-chloro-6-                                                                            1:1  "       Ammonium                                                                             1:1  0                       aniline sulfate        acetylamino          persulfate                                                phenol                                               35 2-methyl-4-amino-5-methoxy-N--(β-amino-                                                          2,6-dimeth-                                                                            1:1  Ethanol-water                                                                          Ammonium                                                                             2:1  0                       ethyl) aniline trihydrochloride                                                                       yl-3-amino           persulfate                                                phenol hy-                                                                     drochloride                                          36 2-methyl-4-amino-N--(β-mesylaminoethyl)                                                          2-methyl-5-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                       aniline sulfate        acetylamino          persulfate                                                phenol                                               37 2-methyl-4-amino-N--(acetylaminoethyl)                                                                3-ureido                                                                               1:1  "       Ammonium                                                                             2:1  0                       aniline sulfate        phenol               persulfate                      38 2-methyl-4-amino-N--carbamylmethyl                                                                    2,6-dimethyl-                                                                          1:1  Water   Ammonium                                                                             2:1  0                       aniline hydrobromide   3-acetyl-            persulfate                                                amino phenol                                         39 2-chloro-4-amino-N--(γ-morpholinopropyl)                                                        3-chloro-6-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  20                      aniline trihydrochloride                                                                              acetylamino          persulfate                                                phenol                                               40 N--methyl paraphenylenediamine dihydro-                                                               2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             2:1  15                      chloride               yl phenol            persulfate                      41 2-methyl-4-amino-N--methyl aniline sulfate                                                            2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             2:1  10                                             yl-3-acetyl-         persulfate                                                amino phenol                                         42 3-methyl-4-amino-N--methylaniline dihydro-                                                            2,6-dimeth-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             1:1  5                       chloride               yl-5-acetyl- water   persulfate                                                amino phenol                                         43 2-methyl-4-amino-N--methylaniline sulfate                                                             2,6-dimethyl                                                                           1:1  acetone-water                                                                          Ammonium                                                                             2:1  15                                             phenol               persulfate                      44 Monohydrate of 3-methyl-4-amino-                                                                      2,6-dimethyl                                                                           1:1  "       Ammonium                                                                             2:1  5                       N--methylaniline dihydrochloride                                                                      phenol               persulfate                      45 3-methoxy-4-amino-N--(β-hydroxyethyl)                                                            2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  15                      aniline sulfate        acetylamino                                                                    phenol                                               46 2-chloro-4-amino-N--(β-acetylaminoethyl)                                                         3-methoxy                                                                              1:1  "       Ammonium                                                                             2:1  0                       aniline sulfate        phenol               persulfate                      47 N--(β-mesylaminoethyl)paraphenylenediamine                                                       2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             1:1  5                       sulfate                yl-3-acetyl-         persulfate                                                amino phenol                                         48 N--(β-hydroxyethyl)paraphenylenediamine                                                          2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  5                       sulfate                acetylamino          persulfate                                                phenol                                               49 2-methoxy-4-amino-N--(β-hydroxyethyl)                                                            2,6-dimethyl                                                                           1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  10                      aniline sulfate        phenol       water   persulfate                      50 2-chloro-4-amino-N--(γ-morpholino propyl)                                                       2-bromo-5-                                                                             1:1  Acetone-water                                                                          Ammonium                                                                             2:1  20                      aniline trihydrochloride                                                                              amino phenol         persulfate                      51 3-methoxy-4-amino N--methylaniline dihy-                                                              2,6-dimeth-                                                                            1:0.85                                                                              "       Ammonium                                                                             2:1  0                       drochloride            yl-5-acetyl-         persulfate                                                amino phenol                                         52 3-methoxy-4-amino-N--methylaniline dihy-                                                              2-methyl-5-                                                                            1:0.85                                                                              Isopropanol-                                                                           Potassium                                                                            2:1  0                       drochloride            acetylamino  water   ferricyanide                                              phenol                                               53 Dihydrate of 2-methoxy-4-amino-N--methyl-                                                             2,6-dimeth-                                                                            1:1  Water   Ammonium                                                                             2:1  0                       aniline sulfate        yl-5-amino           persulfate                                                phenol                                               54 3-methoxy-4-amino-N--methylaniline dihy-                                                              2-methyl-5-                                                                            1:0.85                                                                              Water-  Potassium                                                                            2:1  0                       drochloride            amino phenol isopropanol                                                                            ferricyanide                    55 2-chloro-4-amino-N--methylaniline sulfate                                                             2-methyl-5-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  10                                             acetylamino          persulfate                                                phenol                                               56 2-chloro-4-amino-N--methylaniline sulfate                                                             2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             2:1  5                                              yl-5-acetyl-         persulfate                                                phenol                                               57 2-chloro-4-amino-N--methylaniline sulfate                                                             2,6-dimethyl                                                                           1:1  "       Ammonium                                                                             2:1  10                                             phenol               persulfate                      58 2-chloro-4-amino-N--methylaniline sulfate                                                             2,6-dimeth-                                                                            1:1.10                                                                              "       H.sub.2 O.sub.2                                                                      8:1  20                                             yl-5-amino                                                                     phenol hydro-                                                                  chloride                                             59 2-chloro-4-amino-N--methylaniline sulfate                                                             2-methyl-5-                                                                            1:1.10                                                                              "       "     8:1  20                                             amino phenol                                         60 Monohydrate of 3-chloro-4-amino-N--methyl-                                                            2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             2:1  5                       aniline dihydrochloride                                                                               yl-5-                persulfate                                                acetylamino                                                                    phenol                                               61 Monohydrate of 3-chloro-4-amino-N--methyl-                                                            2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             1:1  5                       aniline dihydrochloride                                                                               yl-5-amino           persulfate                                                phenol                                                                         hydrochlor-                                                                    ide                                                  62 Monohydrate of 3-chloro-4-amino-N--methyl-                                                            2-methyl-6-                                                                            1:1  "       Ammonium                                                                             1:1  5                       aniline dihydrochloride                                                                               amino phenol         persulfate                      63 Monohydrate of 3-chloro-4-amino-N--methyl-                                                            2-methyl-5-                                                                            1:0.65                                                                              "       Ammonium                                                                             2:1  5                       aniline dihydrochloride                                                                               acetylamino          persulfate                                                phenol                                               64 Dihydrate of 2-methoxy-4-amino-N--methyl-                                                             2,6-dimethyl-                                                                          1:1  "       Ammonium                                                                             1:1  0                       aniline sulfate        5-acetyl-            persulfate                                                amino phenol                                         65 3-chloro-4-amino-N--methylaniline dihydro-                                                            2-methyl-5-                                                                            1:1  Ethanol-water                                                                          Ammonium                                                                             1:1  0                       chloride               N--β-hydroxy-   persulfate                                                ethylamino                                                                     phenol                                               66 3-methoxy-4-amino-N--methylaniline dihy-                                                              2,6-dimethyl                                                                           1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                       drochloride            phenol               persulfate                      67 3-methoxy-4-amino-N--methylaniline dihy-                                                              2,6-dimeth-                                                                            1:0.85                                                                              "       Ammonium                                                                             1.75:1                                                                              0                       drochloride            yl-5-amino-          persulfate                                                phenol hy-                                                                     drochloride                                          68 Monohydrate of 3-methyl-4-amino-                                                                      2-methyl-                                                                              1:1  "       Ammonium                                                                             2:1  0                       N--methylaniline dihydrochloride                                                                      5-amino              persulfate                                                phenol                                               69 Monohydrate of 3-methyl-4-amino-N--methyl-                                                            2,6-di- 1:1  "       Ammonium                                                                             2:1  5                       aniline dihydrochloride                                                                               methyl-5-            persulfate                                                amino phenol                                                                   hydro-                                                                         chloride                                             70 3-chloro-4-amino-N--methylaniline dihydro-                                                            2,6-di- 1:1  "       Ammonium                                                                             2:1  5                       chloride               methyl               persulfate                                                phenol                                               71 Monohydrate of 3-methyl-4-amino-N--methyl-                                                            2-methyl-                                                                              1:1  "       Ammonium                                                                             1:1  5                       aniline dihydrochloride                                                                               5-acetyl-            persulfate                                                amino phenol                                         72 2-methyl-4-amino-N--methylaniline sulfate                                                             2,6-di- 1:1  "       Ammonium                                                                             1:1  5                                              methyl-5-            persulfate                                                amino phenol                                                                   hydro-                                                                         chloride                                             73   "                    2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  10                                             acetylamino          persulfate                                                phenol                                               74   "                    2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  10                                             amino phenol         persulfate                      75 4-amino-N--methylaniline dihydrochloride                                                              2-methyl-5-                                                                            1:1  "       Ammonium                                                                             1:1  0                                              acetylamino          persulfate                                                phenol                                               76 2-methoxy-4-amino-N--methylaniline sulfate                                                            2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  0                                              carbethoxy-          persulfate                                                amino phenol                                         77 2-chloro-4-amino-N--methylaniline sulfate                                                             2-methyl-5-                                                                            1:1  Propanol-water                                                                         Ammonium                                                                             2:1  0                                              ureido               persulfate                                                phenol                                               78 2-chloro-4-amino-N--β-hydroxyethylaniline                                                        2,6-dimethyl                                                                           1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                       sulfate                3-ureido             persulfate                                                phenol                                               79 2-chloro-4-amino-N--β-hydroxyethylaniline                                                        3-ureido                                                                               1:1  "       Ammonium                                                                             2:1  0                       sulfate                phenol               persulfate                      80 2-chloro-4-amino-N--β-hydroxyethylaniline                                                        3-acetyl-                                                                              1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0                       sulfate                amino phenol water   persulfate                      81 2-chloro-4-amino-N--β-hydroxyethylaniline                                                        2-methyl-5-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0                       sulfate                acetylamino  water   persulfate                                                phenol                                               82 2-chloro-4-amino-N--β-hydroxyethylaniline                                                        2-methyl-5-                                                                            1:1  Isopropanol-                                                                           Ammonium                                                                             2:1  0-5                     sulfate                ureido       water   persulfate                                                phenol                                               83 4-amino N--methylaniline dihydrochloride                                                              2-methyl 5-                                                                            1:1  Acetone-water                                                                          Ammonium                                                                             2:1  0                                              carbamylme-          persulfate                                                thylamino                                                                      phenol                                               84 3-methyl-4-amino-N--methylaniline dihy-                                                               2-methyl 5-                                                                            1:1  "       Ammonium                                                                             2:1  0                       drochloride            carbamylme-          persulfate                                                thylamino                                                                      phenol                                               85 2-methyl-4-amino-N--methylaniline dihy-                                                               2-methyl 5-                                                                            1:1  "       Ammonium                                                                             2:1  0                       drochloride            carbamylme-          persulfate                                                thylamino                                                                      phenol                                               86 2-chloro-4-amino-N--(acetylaminoethyl)                                                                2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  0-5                     aniline sulfate        carbamylme-          persulfate                                                thylamino                                                                      phenol                                               87 2-chloro-4-amino-N--mesylaminoethyl-                                                                  2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  5                       aniline sulfate        carbamylme-          persulfate                                                thylamino                                                                      phenol                                               88 4-amino-N--β-hydroxyethylaniline sulfate                                                         2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  0                                              carbamylme-          persulfate                                                thylamino                                                                      phenol                                               89 2-methyl-4-amino-N--mesylaminoethylaniline                                                            2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  5                       sulfate                carbamylme-          persulfate                                                thylamino                                                                      phenol                                               90 2-chloro-4-amino-N--methylaniline sulfate                                                             2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  0                                              carbamylme-          persulfate                                                thylamino                                                                      phenol                                               91 2-chloro-4-amino-N--(mesylaminoethyl)                                                                 2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  0                       aniline sulfate        ureido               persulfate                                                phenol                                               92 2-chloro-4-amino-N--(mesylaminoethyl)                                                                 3-ureido                                                                               1:1  "       Ammonium                                                                             2:1  5                       aniline sulfate        phenol               persulfate                      93 2-chloro-4-amino-N--(methylaniline sulfate)                                                           3-acetyl-                                                                              1:1  "       Ammonium                                                                             2:1  5                                              amino phenol         persulfate                      94 2-methyl-4-amino N--ethylaniline sulfate                                                              2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  5                                              acetylamino          persulfate                                                phenol                                               95 2-chloro-4-amino-N--β-hydroxy-ethylaniline                                                       2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             1:1  0                       sulfate                yl-3-acetyl-         persulfate                                                amino phenol                                         96 2-chloro-4-amino-N--methylaniline sulfate                                                             2,6-dimeth-                                                                            1:1  "       Ammonium                                                                             2:1  5                                              yl-3-ureido          persulfate                                                phenol                                               97 2-chloro-4-amino-N--β-hydroxyethylaniline                                                        2-methyl-5-                                                                            1:1  "       Ammonium                                                                             2:1  0                       sulfate                N--carbamyl-         persulfate                                                methylamino                                                                    phenol                                               98 2-chloro-4-amino-N--mesylaminoethylaniline                                                            3-acetyl-                                                                              1:1  "       Ammonium                                                                             2:1  5                       sulfate                amino phenol         persulfate                      99 2-chloro-4-amino-N--methylaniline sulfate                                                             3-ureido                                                                               1:1  "       Ammonium   5                                              phenol               persulfate                      __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     (11) (12)                                                                               (13)                                                                               (14)      (15) (16)                                                                              (17)                                                                              (18)   (19)                                  EX.  DYE     POLYMER              ALCOHOL   (20)                                                                              (21) (22)                       No   Ex. No                                                                             Wt. %                                                                              Type      M.W. (cps)                                                                             %  Type   %  pH Hair Color                      __________________________________________________________________________                                                         Achieved                   M 1  10  0.5 VA/CA 90/10                                                                              10,000  2  Ethanol                                                                               50 7.8                                                                               B 95 (1)                                                                            violine                    M 2   4  0.1   "       10,000  1  "      36 8.1                                                                               D (2)                                                                               silvery glycine            M 3   5  0.05                                                                               PVP       40,000  2  Isopropanol                                                                           25 9  D    parme                      M 4  12  0.008                                                                              VA/CA 90/10                                                                              10,000  2  Ethanol                                                                               50 8.1                                                                               D    pale pearly rose                                                               mauve                      M 5  15  0.025                                                                              VP/VA 30/70                                                                              160,000 2  "      40 8.8                                                                               D    emerald green              M 6  19  0.004                                                                              VA/CA 90/10                                                                              25,000  1  "      36 8.4                                                                               D    light pink blonde          M 7   2  0.05                                                                               PVP       160,000 2  Isopropanol                                                                           25 9  D    pearly mauve               M 8  17  0.01                                                                               VP/VA 60/40    4  2  "      35 9.6                                                                               D    very light silver          M 9   1  0.05                                                                               VA/CA 90/10                                                                              25,000  1  Ethanol                                                                               20 9.5                                                                               D    pale silvery mauve         M 10 18  0.1 VP/CA 30/70                                                                              160,000 2  "      40 10.2                                                                              D    pearly turquoise                                                               blue                       M 11  5  0.002                                                                                "       "       2  "      40 5.7                                                                               D    light pink blond           M 12 18  0.1   "       "       2  "      40 10.2                                                                              B 95 silvery eucalyptus                                                             green                      M 13 14  0.1 VA/CA 90/10                                                                              25,000  1  "      36 8.5                                                                               D    very luminous                                                                  gentian                    M 14 10  0.2   "       25,000  2  "      50 7.4                                                                               D    purple                     M 15  3  0.1 VP/VA 60/40    3.3                                                                               2  Isopropanol                                                                           35 9.8                                                                               B 95 beige grey with                                                                violet                                                                         glints                     M 16 16  0.02                                                                               VP/VA 70/30                                                                              40,000  3  Ethanol                                                                               25 8.7                                                                               D    ice-blue                   M 17 10  0.002                                                                                "       "       3  "      25 10.1                                                                              "    pearly pale pink           M 18  9  0.015                                                                              VP/VA 30/70                                                                              160,000 2  "      40 9.3                                                                               "    pearly light blue          M 19 13  0.013                                                                              VP/VA 60/40    3.7                                                                               2  Isopropanol                                                                           35 9.3                                                                               "    light turquoise blue       M 20  6  0.05                                                                               MM/StM/DEM     8  2.5                                                                               Ethanol                                                                               30 8  "    deep violet pink                        20/23/57                                                          M 21 18  0.1 VP/VA 30/70                                                                              160,000 2  "      40 10.2                                                                              "    deep chestnut with                                                             bronze glints                   14  0.05                                                                  M 22 10  0.1 VA/CA 90/10                                                                              50,000  2  "      50 6.7                                                                               D    deep violet                     C.sub.1 (3)                                                                        0.08                                                                       14  0.05                                                                  M 23 10  0.002                                                                              VA/CA 90/10                                                                              70,000  2  "      50 7.5                                                                               D    golden light                                                                   chestnut                        C.sub.1 (3)                                                                        0.15                                       with violet glints              C.sub.2 (4)                                                                        0.12                                                                  M 24  7  0.2 MM/StM/DEM     12 2.5                                                                               "      30 10.5                                                                              B 95 tin grey with light                                                            violet glints              M 25 28  0.09                                                                               VA/CA 90/10                                                                              25,000  2  "      50 6.3                                                                               D    silvery glycine            M 26 30  0.09                                                                               VP/VA 60/40    4  2  Isopropanol                                                                           35 8.1                                                                               D    silvery blue grey          M 27 20  0.009                                                                              VP/VA 70/30                                                                              40,000  3  Ethanol                                                                               25 8.5                                                                               D    pearly light green         M 28 34  0.02                                                                               VP/VA 60/40    4  2  Isopropanol                                                                           35 9.4                                                                               D    pearly light blue          M 29 32  0.02                                                                                 "            3.3                                                                               2  "      35 5.5                                                                               D    light parme                M 30 31  0.05                                                                                 "            3.7                                                                               2  "      35 9  D    silvery grey with                                                              mauve glints               M 31 23  0.015                                                                              PVP       360,000 2  "      25 8.9                                                                               D    light green with                                                               golden glints              M 32 33  0.025                                                                              VA/CA 90/10                                                                              50,000  1  Ethanol                                                                               36 5.5                                                                               D    pearly light blue          M 33 25  0.5   "       50,000  2  "      50 10.1                                                                              B 95 metallic grey              M 34 35  0.05                                                                                 "       70,000  1  "      36 9.2                                                                               D    silvery pale mauve         M 35 21  0.05                                                                                 "       50,000  2  "      50 7  D    silvery blue grey          M 36 36  0.06                                                                                 "       "       2  "      50 8.8                                                                               D    pearly grey                M 37 37  0.065                                                                              VP/CA 60/40    3.3                                                                               2  Isopropanol                                                                           35 9.3                                                                               B 95 dark blue grey             M 38 27  0.05                                                                               MM/StM/DEM (5) 2.5                                                                               2.5                                                                               Ethanol                                                                               30 10.3                                                                              D    pink beige grey            M 39 24  0.1 VA/CA 90/10                                                                              50,000  2  "      50 6.4                                                                               D    very luminous deep                                                             violet                     M 40 26  0.033                                                                              VP/CA 70/30                                                                              40,000  3  "      25 6.7                                                                               D    pearly light blue          M 41 22  0.09                                                                               VP/CA 30/70                                                                              160,000 2  "      40 9.7                                                                               B 95 metallic grey              M 42 21  0.002                                                                              PVP       360,000 2  Isopropanol                                                                           25 10.3                                                                              D    very light silver                                                              with                                                                           blue glints                M 43 29  0.045                                                                              MM/StM/DEM (5) 8  2.5                                                                               Ethanol                                                                               30 9  D    tamarisk pink              M 44 39  0.3 PVP       40,000  2  Isopropanol                                                                           25 5.5                                                                               D    deep royal blue            M 45 38  0.1 VA/CA 90/10                                                                              70,000  1  Ethanol                                                                               36 9  B 95 silvery grey with                                                              mauve glints                    36  0.1                                                                   M 46 22  0.2 VA/CA 90/10                                                                              "       2  "      50 7  B 95 steel grey                      C.sub.3 (5a)                                                                       0.02                                                                       C.sub.4 (6)                                                                        0.03                                                                  M 47 57  0.25                                                                               VP/VA 60/40    3.7                                                                               2  Isopropanol                                                                           35 8.5                                                                               D    silvery pale violet        M 48 60  0.1   "            4  2  "      35 5.5                                                                               D    silvery grey with                                                              light                                                                          mauve glints               M 49 69  0.3 VA/CA 90/10                                                                              45,000  2  Ethanol                                                                               50 5  D    violine                    M 50 99  0.35                                                                                 "       "       2  "      50 7  B 95 metallic grey              M 51 94  0.1   "       "       2  "      50 6.5                                                                               D    very light pearly                                                              blue                       M 52 66  0.35                                                                                 "       "       2  "      50 7  D    royal blue                 M 53 92  0.15                                                                               VP/VA 70/30                                                                              40,000  3  "      25 8  D    pearly pink beige          M 54 91  0.15                                                                               VA/CA 90/10                                                                              50,000  1  "      36 7  D    lilac                      M 55 65  0.3   "       "       2  "      50 9.5                                                                               D    violet beige               M 56 75  0.1 VP/VA 60/40    4  2  Isopropanol                                                                           35 5  D    silvery blue               M 57 63  0.05                                                                                 "            4  2  "      35 10.5                                                                              D    cyclamen pink              M 58 59  0.035                                                                                "            3.5                                                                               2  "      35 6  D    salmon pink                M 59 53  0.05                                                                               VP/VA 30/70                                                                              160,000 2  Ethanol                                                                               40 6  D    beige shaded mauve         M 60 67  0.09                                                                                 "       "       2  "      40 8.5                                                                               D    pearly glycine             M 61 61  0.07                                                                               VP/VA 60/40    3.7                                                                               2  Isopropanol                                                                           35 9.5                                                                               D    pearly pale pink           M 62 71  0.03                                                                               VP/VA 30/70                                                                              160,000 2  Ethanol                                                                               40 8.5                                                                               D    pearly myosotis blue       M 63 76  0.05                                                                                 "       "       2  "      40 10 D    light blue grey            M 64 72  0.2   "       "       2  "      40 4.5                                                                               D    purple                     M 65 73  0.1   "       "       2  "      40 5  D    silvery lavender                                                               blue                       M 66 88  0.2 VP/VA 70/30                                                                              40,000  3  "      20 8.5                                                                               D    silvery grey violet             26  0.15                                                                  M 67 62  0.025                                                                              VA/CA 90/10                                                                              70,000  1  "      35 7  D    pink beige                 M 68 64  0.15                                                                                 "       10,000  2  "      50 7  D    myosotis blue              M 69 68  0.13                                                                                 "       50,000  1  "      36 4.5                                                                               D    violet pink                M 70 58  0.05                                                                                 "       "       2  "      50 8.5                                                                               D    very luminous salmon                                                           pink                       M 71 51  0.1   "       "       1  "      36 7  D    silvery grey blue          M 72 89  0.1 VP/VA 60/40    3.7                                                                               2  Isopropanol                                                                           35 4  D    silvery glycine            M 73 88  0.1 PVP       40,000  2  "      25 9  B 95 metallic grey with                                                             mauve glints               M 74 87  0.05                                                                               VP/VA 30/70                                                                              160,000 2  Ethanol                                                                               40 8.5                                                                               D    golden pale pink           M 75 86  0.075                                                                              VP/VA 70/30                                                                              40,000  3  "      25 6.5                                                                               D    eglatine                   M 76 85  0.05                                                                               VP/VA 60/40    4  2  Isopropanol                                                                           35 4  D    glycine                    M 77 98  0.1 VP/VA 30/70                                                                              160,000 2  Ethanol                                                                               40 7  D    light silver               M 78 56  0.2 VA/CA 90/10                                                                              70,000  1  "      36 9  D    mauve                      M 79 50  0.2   "       50,000  1  "      36 5.5                                                                               D    violet                     M 80 81  0.2 VP/VA 30/70                                                                              160,000 2  "      40 4  D    light grey with                                                                mauve                                                                          glints                     M 81 79  0.075                                                                              VA/CA 90/10                                                                              50,000  1  "      50 7  D    light silvery grey                                                             shaded mauve               M 82 54  0.1   "       50,000  1  "      50 7  D    violet blue                M 83 45  0.1   "       70,000  1  "      36 8  D    silvery myosotis                                                               blue                       M 84 46  0.1   "       70,000  1  "      36 9  D    pearly mauve               M 85  8  0.2 VP/VA 30/70                                                                              160,000 2  "      40 8  D    tamarisk pink              M 86 42  0.1 VA/CA 90/10                                                                              70,000  2  "      50 6.5                                                                               D    silvery blue grey          M 87 44  0.3   "       70,000  2  "      50 6  D    lavender                   __________________________________________________________________________                                                         blue                        (1) B 95 = 95% natural white hair                                              (2) D = bleached hair                                                          (3) C.sub.1 = N[(4hydroxy)-phenyl2,6-dimethyl benzoquinoneimine                (4) C.sub.2 = 4nitro-N,N--dihydroxyethylaniline                                (5) Terpolymer of methyl methacrylate (20%)stearyl methacrylate (23%)          dimethylaminoethyl methacrylate (57%) quaternized with dimethyl sulfate        and having a viscosity of 8-12 cps, at 5% in dimethylformamide and at the      boiling temperature of ether.                                                  (5a) C.sub.3 = Nitroortho pphenylenediamine                                    (6) C.sub.4 = lamino propylamino anthraquinone                           

                                      TABLE IV                                     __________________________________________________________________________     (31)                                                                              (32) (33)                                                                               (34)    (35)                                                                               (36)   (37)                                                                               (38)  (39)                                                                               (40)                                                                              (41) (42)                                  Surface active                                                                 agent       SOLVENT    OTHER ADJUVANTS                             EX.                                                                               DYE              wt.        wt.       wt.                                   No EX. No                                                                              Wt. %                                                                              Type    %   Type   %   Type  %   pH Hair Color                     __________________________________________________________________________                                                          achieved                  T 1                                                                                1   0.53            Isopropanol                                                                           40            11 D (10)                                                                              silver with                                                                    mauve glints              T 2                                                                                2   0.04            MEDG (1)                                                                               5            9  D    silvery mauve grey                                Ethanol                                                                               25                                              T 3                                                                               15   0.077           Ethanol                                                                               23  CMC (2)                                                                              3.9 10.4                                                                              D    emerald green             T 4                                                                                5       AL 10.5OE (3)                                                                          5   Butylglycol                                                                            5            6  D    light pink blond          T 5                                                                               16   0.6                                                                       2    0.5                                                                       C1 (4)                                                                              0.05                                                                                 "     20                       8.5                                                                               D    pink beige                   C2 (5)                                                                              0.07                                                                   T 6                                                                                3   0.30                                                                               LSS 19 (6)                                                                             20             EDTA (7)                                                                             2   10.6                                                                              D    silvery grey with                                                              blue glints               T 7                                                                                9   0.06            Ethanol                                                                               20  CMC   4   8  D    pearly light                                                                   turquoise blue            T 8                                                                               18   0.2 NP 4OE (8)                                                                             10                                                                     NP 9OE (9)                                                                             10                       5.6                                                                               B 95 (11)                                                                           vervain                   T 9                                                                               10   0.1 ALS (12)                                                                               10                       9.7                                                                               D    pearly light mauve                                                             pink                      T 10                                                                              16   0.1   "     10                       10.5                                                                              D    pearly light green        T 11                                                                               6   0.33            Ethanol                                                                               30  CMC   3   10.5                                                                              B 95 silvery violet            T 12                                                                               4   0.4 AL 10.5OE                                                                              20                       10   "  eucalyptus green          T 13                                                                              15   0.1 LSS 19  20             EDTA  2   10.5                                                                              D    mahogany                     C3 (14)                                                                             0.08                                                                      C4 (15)                                                                             0.10                                                                      C5 (16)                                                                             0.04                                                                   T 14                                                                              11   0.025           Isopropanol                                                                           50  "Carbopol                                                                            2.38                                                                               6  D    light green                                                  934" (17)                                   T 15                                                                              27   0.07                                                                               LSS 19  20             EDTA  0.2 10.7                                                                              D    light beige grey          T 16                                                                              23   1   NP 9OE 10                                                                              "   15               5.5 B 95                                                                              petroleum blue                 T 17                                                                              20   0.7 DFAC (13)                                                                              7.5 Ethanol                                                                               25            7    "  eucalyptus green          T 18                                                                              32   0.1             "      20            10.5                                                                              D    pearly pink beige                                 MEDG   10                                              T 19                                                                              23   0.30                                                                               NP 4OE  8.5                      9  B 95 light chestnut with          20   0.35                                                                               NP 9OE  8.5 Ethanol                                                                               15                    copper glints                C6 (18)                                                                             0.03                                                                      C7 (19)                                                                             0.1                                                                    T 20                                                                              24   0.4             Ethanol                                                                               40            9  D    deep violet blue          T 21                                                                              37   1.1             "      45            9.5                                                                               D    myosotis blue             T 22                                                                              33   0.8             "      20  CMC   4   5.5                                                                               D    silvery light blue        T 23                                                                              37   0.3                                                                       24   0.2             "      40            10.5                                                                              B 95 silvery mauve gray           C2 (5)                                                                              0.09                                                                      C8 (20)                                                                             0.05                                                                   T 24                                                                              26   0.65            "      33  "Carbopol                                                                            3   10 D    light emerald green                                          934" (17)                                   T 25                                                                              25   0.22                                                                               NP 9OE  10  Butylglycol                                                                            5            5.5                                                                               D    platinum with light                                                            blue glints               T 26                                                                              34   2   DFAC (13)                                                                              6.5 Ethanol                                                                               35            10.5                                                                              D    pearly light                                                                   turquoise blue            T 27                                                                              43   0.4 AL 10.5OE                                                                              5   Butylglycol                                                                            5            7  D    very silvery pale                     (3)                                      blue                      T 28                                                                              40   0.25                                                                               DFAC (13)                                                                              10                       9.5                                                                               D    pearly pastel blue        T 29                                                                              48   0.2 ALS (12)                                                                               10                       9  D    ice blue                  T 30                                                                              49   0.4                        "Carbopol                                                                            4.76                                                                               9.5                                                                               D    pearly pastel blue                                           934" (17)                                   T 31                                                                              47   0.4 LSS 19 (6)                                                                             20             EDTA  0.2 12 D    light bluish silver       T 32                                                                              41   0.05                       CMC (2)                                                                              5   10 D    very light pearly                                                              blue                      T 33                                                                              90   0.5 AL 10.5OE (3)                                                                          5                        9  D    eglantine pink            T 34                                                                              95   0.35                                                                               LSS 19 (6)                                                                             20             EDTA (7)                                                                             0.2 10 D    light silver grey         T 35                                                                              93   0.3                        CMC (2)                                                                              5   9  D    light blue grey           T 36                                                                              96   0.3             MEDG (1)                                                                              10            5  D    silvery mauve             T 37                                                                              97   0.4 DFAC (13)                                                                              10                       9  D    very light pink                                                                blond                     T 38                                                                              78   0.5 LSS 19 (6)                                                                             20             EDTA (7)                                                                             0.2 10 D    mauve                     T 39                                                                              52   0.15            Ethanol                                                                               25            9  D    light turquoise                                                                blue                      T 40                                                                              70   0.6   "     20               "   0.2 11 D    pearly light                                                                   beige grey                T 41                                                                              84   0.35            "      20  "Carbopol                                                                            3.6 10 D    silvery pale                                                 934" (17)         mauve                     T 42                                                                              83   0.35                                                                               ALS (12)                                                                               5                        9.2                                                                               D    light silver gray                                                              with mauve glints         T 43                                                                              74   0.6 DFAC (6)                                                                               2   "      30            10.5                                                                              B 95 metallic grey                                                                  with mauve glints         T 44                                                                              55   0.8 NP 4OE (8)                                                                             8   "       2            11 D    light silver grey                     NP 9OE (9)                                                                             8                                with mauve glints         T 45                                                                              80   0.4 AL 10.5OE (3)                                                                          5   Butylgly-                                                                              5            9  D    silvery light blue                                col                          grey                      T 46                                                                              77   0.5 AL 10.5OE (3)                                                                          20                       4  D    pearly light parme        T 47                                                                              82   0.2             Propylene                                                                              5  CMC (2)                                                                              4   8  D    light pink ash                                    glycol                       beige                     T 48                                                                              93   0.2             Ethanol                                                                               50    "   2.5 10 B 95 metallic grey                87   0.5                                          shaded violet                35   0.1                                                                    __________________________________________________________________________      (1) MEDG = monomethyl ether of diethyleneglycol                                (2) CMC = Carboxymethylcellulose                                               (3) AL 10.5OE = laurylalcohol oxyethylenated with 10.5 moles of ethylene       oxide                                                                          (4) C1 = 2methoxy-4-nitro-hydroxyethylaniline                                  (5) C2 = 1aminopropylamino anthraquinone                                       (6) LSS 19 = mixture consisting of 19% laurylalcohol oxyethylenated with       moles of ethylene oxide and 81% of sodium sulfate salt of the same             oxyethylenated alcohol                                                         (7) EDTA = ethylene diamine tetraacetic acid                                   (8) NP 4OE = Nonylphenol oxyethylenated with 4 moles of ethylene oxide         (9) NP 9OE = Nonylphenol oxyethylenated with 9 moles of ethylene oxide         (10) D = bleached hair                                                         (11) B 95 = 95% naturally white hair                                           (12) ALS = ammonium laurylsulfate                                              (13) DFAC = diethanolamides of fatty acids of copra                            (14) C3 = N--[(4hydroxy)-phenyl2,6-dimethyl benzoquinoneimine                  (15) C4 =  N[(4amino)phenyl2-methyl-5-amino benzoquinoneimine                  (16) C4 = Nitroorthophenylenediamine                                           (17) "Carbopol 934" = Polymer of acrylic acid having a molecular weight        between 2-3 million                                                            (18) C6 = N[(4ethylamino)-phenyl2-methyl-5-acetylamino benzoquinoneimine       (19) C7 = nitroparaphenylenediamine                                            (20) C8 = 3nitro-4(hydroxyethyl) amino anisole                            

We claim:
 1. An indoaniline dye of the formula ##STR9## wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, acetylamino and ureido with the proviso that at least one of R₁ and R₄ represents a member selected from the group consisting of chlorine, bromine, ureido and acetylamino;R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, amino, N-alkylamino, N-(hydroxyalkyl)-amino, N-(carbamylalkyl)-amino, acetylamino and ureido, each of said alkyl moieties containing 1 to 6 carbon atoms; R₅ and R₆ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6carbon atoms and alkoxy having 1 to 6 carbon atoms with the proviso that when R₅ and R₆ are both other than hydrogen at least one is in a meta-position relative to the NHR₇ ; and R₇ represents a member selected from the group consisting of hydroxyalkyl, acetylaminoalkyl, mesylaminoalkyl, carbamylalkyl and aminoalkyl, each of said alkyl moieties containing 1 to 6 carbon atoms.
 2. An indoaniline dye of the formula ##STR10## wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, acetylamino and ureido with the proviso that at least one of R₁ and R₄ represents a member selected from the group consisting of chlorine, bromine, methyl, ureido and acetylamino,R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, amino, N-alkylamino, N-(hydroxyalkyl)-amino, N-(carbamylalkyl)-amino, acetylamino and ureido, each of said alkyl moieties containing 1 to 6 carbon atoms; R₅ and R₆ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms and alkoxy having 1 to 6 carbon atoms with the proviso that when R₅ and R₆ are both other than hydrogen at least one is in a meta-position relative to the NHR₇ ; and R₇ represents a member selected from the group consisting of acetylaminoalkyl, mesylaminoalkyl, carbamylalkyl and aminoalkyl, each of said alkyl moieties containing 1 to 6 carbon atoms.
 3. N-[(4'-β-hydroxyethylamino-3'-chloro)phenyl]-2-methyl-5-ureido benzoquinone imine.
 4. N-[(4'-ethylamino-3'-chloro)phenyl]-2-methyl-5-acetylamino benzoquinoneimine.
 5. N-[(4'-methylamino-3'-chloro)phenyl]-2,6-dimethyl-5-acetylamino benzoquinoneimine.
 6. N-[(4'-methylamino-3'-methyl)phenyl]-2-methyl-5-acetylamino benzoquinoneimine.
 7. N-[(4'-methylamino-3'-chloro)phenyl]-2-methyl-5-ureido benzoquinoneimine. 